US4216332A - Preparation of chlorinated N-methyl-imidazoles and N-methyl-imidazolines - Google Patents

Preparation of chlorinated N-methyl-imidazoles and N-methyl-imidazolines Download PDF

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US4216332A
US4216332A US05/974,411 US97441178A US4216332A US 4216332 A US4216332 A US 4216332A US 97441178 A US97441178 A US 97441178A US 4216332 A US4216332 A US 4216332A
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methyl
chlorinated
imidazolines
imidazoles
sub
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US05/974,411
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English (en)
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Manfred Lenthe
Gerhard Dankert
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/68—Halogen atoms

Definitions

  • the present invention relates to an unobvious process for the preparation of known chlorinated N-methyl-imidazoles and -imidazolines, which are used as intermediate products for the synthesis of tetrachloroethylene-bis-isocyanide dichloride; the latter compound can be used for the production of pesticidally active compounds.
  • N,N-dimethylaminoacetonitrile is, for this purpose, introduced into a chlorinated aliphatic hydrocarbon as the solvent and is chlorinated at temperatures of up to 150° C., if appropriate while irradiating with ultraviolet light.
  • temperature programs are prescribed and, if these are observed, the compounds are synthesized in yields of at most 68% of theory.
  • n represents the number 0 or 1
  • a double bond being present between the C atoms in the 4-position and 5-position in the case where m is 0, and a single bond being present in the case where m is 1
  • N,N-dimethylaminoacetonitrile or its hydrochloride if N,N-dimethylaminoacetonitrile or its hydrochloride is introduced into a mixture of its chlorination products, with simultaneous addition of chlorine gas, in the absence of a solvent, at a temperature between about 70° and 150° C.
  • N-methyl-imidazoles or -imidazolines obtained in the process according to the invention may be further processed by subjecting them to a high temperature chlorination at a temperature range of between about 130° and 220° C., resulting in the desired secondary product tetrachloroethylene-bis-isocyanide dichloride of the formula
  • the chlorinated N-methyl-imidazoles and -imidazolines can be formed in such high yields that the secondary product of the formula (III) is obtained in a yield of 90%, relative to the nitrile of the formula (II) employed.
  • the purity of the secondary product of the formula (III) may be 95 to 99%.
  • N,N-Dimethylaminoacetonitrile of the formula (II), to be used as the starting material is a compound which has been known for a long time. It is prepared from dimethylamine, hydrocyanic acid and formaldehyde; such reactions are generally known by the name of "Mannich reactions" (see, in this context, J. Am. Chem. Soc. 68, 1607 (1946) and Liebigs Ann. Chem. 279, 43 (1894)).
  • reaction temperatures required for the reaction are illustrated in the section dealing with the examples hereinbelow. In general, the reaction is carried out between about 70° and 150° C., preferably between about 90° and 130° C.
  • the chlorinated N-methyl-imidazoles and -imidazolines of the formula (I) obtainable in accordance with the invention include, specifically, the following compounds: ##STR3##
  • the compounds are not, in general, isolated; instead, as already mentioned, the mixture of the chlorinated N-methyl-imidazoles or -imidazolines is subjected to a secondary reaction (chlorination at a high temperature), whereby the compound of the formula (III) is obtained.
  • the last-mentioned compound serves as an intermediate product for the preparation of pesticidally active compounds.
  • the compound (III) gives N,N'-bis-(trifluoromethyl)-tetrafluoroethylenediamine; the latter then gives perfluoro-2,5-diazahexa-2,4-diene, with elimination of 2 mols of hydrogen fluoride, by means of sodium fluoride (see, in this context, DT-AS (German Published Specification) 2,013,433 or U.S. Pat. No. 3,694,507; the compound is obtained by a different method, and is described, by P. H. Ogden and R. A. Mitsch, J. Ann. Chem. Soc. 89, 5008 (1967)).
  • This perfluoro compound undergoes, for example, a cyclization reaction with N-methyl-N'-(4-chlorophenyl)-thiourea to give the plant protection fungicide 2-methylimino-3-(4'-chlorophenyl)-4,5-bis-(trifluoromethylimino)-thiazolidine, known from the literature (see DT-OS (German Published Specification) 2,062,348 or U.S. Pat. No. 3,895,020).
  • dimethylaminoacetonitrile is introduced into a mixture of chlorinated N-methyl-imidazoles and -imidazolines, with simultaneous addition of chlorine via a gas distributor, in such a way that a clear, pale yellow solution can be withdrawn from the reaction space through an outlet.
  • the speed of addition of the nitrile depends on the temperature: at 90° C., about 70 g of nitrile per liter of reaction volume and per hour can be introduced into a bubble column chamber, and at 130° C. as much as about 120 g of nitrile per liter and per hour, without resulting in the formation of a suspension.
  • the stated values depend on the addition of chlorine: the chlorine is employed in excess, and in particular the molar ratio of nitrile of the formula (II) to chlorine is preferably about 1:5 at 90° C. and preferably about 1:6 at 130° C. These values correspond to the experience that at higher temperature the chlorination leads to the formation of more highly chlorinated N-methyl-imidazoles or -imidazolines.
  • the reaction can be carried out discontinuously or, to advantage, continuously. In both cases the same reaction apparatuses can be used, with the difference that in the continuous steady state, the reaction volume is kept constant while in the discontinuous, non-steady state method of operation the reaction volume increases progressively so that, due to the constant space-time yield, the overall reaction rate is also increased progressively.
  • bubble columns operated continuously or discontinuously, in cocurrent or counter-current, in one or more stages, the chamber or chambers of the columns being equipped with heat exchangers in the form of jackets or of tube coils immersed in the liquid.
  • heat exchangers in the form of jackets or of tube coils immersed in the liquid.
  • the introduction of nitrile, relative to the reaction volume, can be approximately doubled compared to a stirred kettle, without resulting in the formation of a suspension.
  • the reaction mixture from the first stage of the process is generally introduced into a stirred kettle or a bubble column and is reacted with chlorine at temperatures from about 130° to 220° C. After 10 to 15 hours, the reaction has ended and the reaction product--fused tetrachloroethylene-bis-isocyanide dichloride--is discharged from the reactor through a suitable device, for example a crystallizing screw.
  • a suitable device for example a crystallizing screw.
  • Another possible way of isolating the product is, for example, to take up the hot reaction melt in a solvent in which the compound is only sparingly soluble, for example carbon tetrachloride, chlorobenzene, 1,2-dichloro-benzene or the like, and to filter off the product.
  • a purification effect is additionally achieved, and the tetrachloroethylene-bis-isocyanide dichloride is obtained as a white mass of crystals, having a melting point of 167° C. (value in the literature: 166° C.).
  • FIG. 1 is a schematic view of an apparatus for carrying out a first stage chlorination
  • FIG. 2 is a schematic view of an apparatus for further chlorinating the product from FIG. 1.
  • chlorine (3) is introduced via a gas distributor plate (5) into the effervescent layer of material, equipped with a heat exchanger (6).
  • N,N-Dimethylaminoacetonitrile (1) is pumped in through a capillary (4) flushed with nitrogen (2).
  • the product can be drained off via an overflow (9).
  • the vapors produced at higher temperatures are very largely condensed in the reflux condenser (7), while such material as breaks through is condensed in the product condenser (8) and taken off at (10) to ensure material balance.
  • the gases (11) which leave the apparatus are freed from chlorine in an absorber and washed with water to remove the hydrogen chloride.
  • the chamber has the following dimensions:
  • volume of liquid 3.0 to 3.5 liters depending on the gassing conditions.
  • the apparatus represented in FIG. 2 is used in the Examples for the high temperature chlorination.
  • This apparatus is an eight-stage counter-current bubble column with heat exchangers (23) built into each individual chamber (21).
  • the chlorinated imidazoles/imidazolines are introduced at the top of the column (24) and run, counter-current to the gas (25) downwards via overflows (22) into the sump of the column, from which the finished product is taken off (27).
  • the gases (26) which issue at the top of the column are first partially condensed (reflux condenser) and are taken up in an absorber (28).
  • the counter-current bubble column shown in FIG. 2 was modified so that the two uppermost chambers were combined into a larger chamber. The result of this was that at a constant space-time yield the rate of conversion was virtually doubled.
  • N,N-dimethylaminoacetonitrile was fed, as in the preceding examples, into an initially introduced mixture consisting of chlorinated N-methyl-imidazoles and -imidazolines, at a rate of 140 g/hr, and was reacted with a stream of 1,500 g/hr of chlorine gas.
  • the chambers of the column were run with the following temperature programs:
  • This example shows that the first chlorination stage can also be carried out in other reactors than a bubble column.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US05/974,411 1978-01-25 1978-12-29 Preparation of chlorinated N-methyl-imidazoles and N-methyl-imidazolines Expired - Lifetime US4216332A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2803037 1978-01-25
DE2803037A DE2803037C2 (de) 1978-01-25 1978-01-25 Verfahren zur Herstellung eines Gemisches von chlorierten N-Methylimidazolen und N-Methyl-imidazolinen

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US (1) US4216332A (fr)
JP (1) JPS54112865A (fr)
BE (1) BE873676A (fr)
DE (1) DE2803037C2 (fr)
GB (1) GB2013195B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4365019A (en) * 1981-08-06 1982-12-21 Eastman Kodak Company Positive-working resist quinone diazide containing composition and imaging method having improved development rates

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1670913U (de) 1953-08-26 1954-01-28 Heinrich Hildner Akustische blinker-kontrollvorrichtung fuer kraftfahrzeuge.
DE1221212B (de) 1961-12-12 1966-07-21 Bayer Ag Verfahren zur Herstellung von Imidchloriden
US3631058A (en) * 1967-08-19 1971-12-28 Bayer Ag Process for the production of chlorinated n-methyl imidazoles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1670913U (de) 1953-08-26 1954-01-28 Heinrich Hildner Akustische blinker-kontrollvorrichtung fuer kraftfahrzeuge.
DE1221212B (de) 1961-12-12 1966-07-21 Bayer Ag Verfahren zur Herstellung von Imidchloriden
US3631058A (en) * 1967-08-19 1971-12-28 Bayer Ag Process for the production of chlorinated n-methyl imidazoles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Beck et al. Angew. Chem. 1974, vol. 86, p. 134. *
Beck et al. Angew. Chem. International Edition in English 1974, vol. 13, p. 210. *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4365019A (en) * 1981-08-06 1982-12-21 Eastman Kodak Company Positive-working resist quinone diazide containing composition and imaging method having improved development rates

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JPS54112865A (en) 1979-09-04
GB2013195A (en) 1979-08-08
GB2013195B (en) 1982-05-19
DE2803037A1 (de) 1979-08-09
BE873676A (fr) 1979-07-24
JPS617186B2 (fr) 1986-03-04
DE2803037C2 (de) 1984-05-17

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